Antibacterial epoxy adhesive and preparation method thereof

Abstract

The invention discloses an antibacterial epoxy adhesive and a preparation method thereof. The antibacterial epoxy adhesive comprises the following components in parts by weight: 100 parts of epoxy resin, 5-50 parts of a curing agent, 0.1-3.0 parts of a coupling agent and 1-30 parts of antibacterial filler, wherein the antibacterial filler comprises an inner core and a shell, the inner core is aluminum oxide, and the shell is formed by polymerizing benzyl bromide, acrylic ester, glycidyl methacrylate, triethylene glycol dimethacrylate and acrylic acid. According to the invention, the epoxy resin, the curing agent, the coupling agent and the polymer-coated alumina antibacterial filler are compounded, so that the prepared epoxy adhesive has good mechanical properties and shows antibacterial ability, and the preparation method is simple and convenient to operate.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to an antibacterial epoxy adhesive and a preparation method thereof. Background Art

[0002] While epoxy adhesives play a bonding role between bonded materials, they can be attacked by microorganisms, lose adhesion, and even cause the adhesive layer to fall off, affecting the bonding strength; at the same time, bacterial plaque on the surface of the adhesive layer can transmit diseases and cause great harm to human health.

[0003] Epoxy resin adhesives have good bonding properties and high waterproof properties, and are widely used in wooden furniture, electronic appliances, etc. However, epoxy resin adhesives have problems such as poor toughness and low mechanical strength, and epoxy resin adhesives do not have antibacterial and mildew-proof properties, while antibacterial epoxy adhesives can avoid the above problems.

[0004] Therefore, it is of great significance to develop an epoxy adhesive with good mechanical properties and antibacterial properties. Summary of the invention

[0005] In view of the above-mentioned shortcomings, the object of the present invention is to provide an antibacterial epoxy adhesive and a preparation method thereof, so as to solve the technical problems of poor mechanical properties and insufficient antibacterial properties of existing epoxy adhesives.

[0006] To achieve the above object, the present invention is implemented through the following technical solutions: In a first aspect, the present invention provides an antibacterial epoxy adhesive, comprising, by weight: 100 parts of epoxy resin, 5-50 parts of curing agent, 0.1-3.0 parts of coupling agent, and 1-30 parts of antibacterial filler; wherein the antibacterial filler comprises an inner core and an outer shell, the inner core is aluminum oxide, and the outer shell is formed by polymerization of benzyl bromide, acrylate, glycidyl methacrylate, triethylene glycol dimethacrylate and acrylic acid.

[0007] At present, antibacterial materials are mainly divided into inorganic antibacterial agents and organic antibacterial agents. Inorganic antibacterial agents use the antibacterial ability of metals such as silver, copper, and zinc to fix metals such as silver, copper, and zinc (or their ions) on the surface of porous materials such as fluorite and silica gel through physical adsorption ion exchange and other methods. Metals such as mercury, cadmium, and lead also have antibacterial ability, but they are harmful to the human body; copper, nickel, and cobalt ions have color, which will affect the appearance of the product. Zinc has certain antibacterial properties, but its antibacterial strength is only 1 / 1000 of silver ions. Organic antibacterial agents mainly include vanillin or ethyl vanillin compounds, as well as acylanilides, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, biguanides, phenols, etc. The safety of organic antibacterial agents is still under study. Generally speaking, organic antibacterial agents have poor heat resistance, are easily hydrolyzed, have a short effective period, and the above antibacterial agents are easy to overflow the surface of the material, causing harm to the human body. The invention uses aluminum oxide as the core and covers the surface with a polymer layer, which can not only improve the antibacterial property of the material but also has higher stability.

[0008] Preferably, the method for preparing the above antibacterial filler comprises the following steps: Mixing benzyl bromide, acrylate and solvent and stirring to react to obtain a first precipitate; uniformly mixing the first precipitate with glycidyl methacrylate, triethylene glycol dimethacrylate and a solvent to obtain a mixed solution; Aluminum oxide, acrylic acid and a solvent are mixed and stirred, and solid-liquid separation is performed to obtain a second precipitate; The second precipitate, the initiator and the mixed solution are mixed and reacted, and the antibacterial filler is obtained after solid-liquid separation.

[0009] Preferably, the mass ratio of benzyl bromide to acrylate is 1:1 to 1:5.

[0010] Preferably, the temperature for stirring the mixture of benzyl bromide, acrylate and solvent is 10-80° C. and the reaction time is 1-24 h.

[0011] Preferably, the mass ratio of the first precipitate, glycidyl methacrylate, and triethylene glycol dimethacrylate is 1:(1-5):(1-5).

[0012] Preferably, the mass ratio of aluminum oxide to acrylic acid is 6:(1-20).

[0013] Preferably, the mass ratio of the second precipitate to the first precipitate in the mixed solution is 1:1 to 1:5.

[0014] Preferably, when the second precipitate, the initiator and the mixed solution are mixed and reacted, the reaction temperature is 10-80° C. and the reaction time is 1-24 h.

[0015] Preferably, the above solvent is an alcohol solvent, such as methanol, ethanol, isopropanol, etc.

[0016] The type of initiator used in the above reaction is not limited, including but not limited to dibenzoyl peroxide, tert-butyl 2-ethylhexanoate, etc. Preferably, the mass ratio of the amount of the initiator to the glycidyl methacrylate in the mixed solution is (0.01-0.05):1.

[0017] Preferably, the epoxy resin is one or more of epoxy resins E-44 and E-51; the curing agent is one or more of ethylenediamine, triethylamine, diethylenetriamine, and triethylenetetramine; and the coupling agent is one or more of silane coupling agents KH-550, KH-560, KH-570, and KH-580.

[0018] In a second aspect, the present invention provides a method for preparing an antibacterial epoxy adhesive, comprising the following steps: uniformly mixing an epoxy resin and a coupling agent to obtain a first material; uniformly mixing the first material and a curing agent to obtain a second material; and uniformly mixing the second material and an antibacterial filler to obtain an antibacterial epoxy adhesive.

[0019] The beneficial effects of the present invention are: The epoxy adhesive prepared by the invention has good mechanical properties and exhibits antibacterial ability by compounding epoxy resin, curing agent, coupling agent and antibacterial filler of polymer-coated alumina, and the preparation method is simple and easy to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solution of the embodiment of the present invention, the drawings of the embodiment are briefly introduced below.

[0021] Figure 1 is the Fourier infrared spectrum of the antibacterial filler prepared in Example 1; Figure 2 is a photograph of the antibacterial filler and aluminum oxide prepared in Example 1 in a methyl methacrylate / water solution. DETAILED DESCRIPTION

[0022] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1 (1) Preparation of antibacterial filler: Add 10 g of acrylate to a conical flask, then add 10 g of benzyl bromide, add 20 ml of methanol, put in a magnet, cover with a lid, stir on a magnetic stirrer, and a large amount of white solid precipitate will appear. Stop stirring. Overnight, all will become white solid precipitate. Use a shovel to transfer the solid sample to a sample bottle, wash it twice with a small amount of ether, shake it, and let it stand until the supernatant appears. Pour out the supernatant, wrap the bottle with paper, and place it on the table to dry for a few hours to allow the solvent to evaporate. Then transfer the sample bottle to a vacuum oven and vacuum dry it overnight to obtain the first precipitate after washing and drying.

[0024] The first precipitate was mixed with glycidyl methacrylate, triethylene glycol dimethacrylate and ethanol in a mass ratio of 1:1:1 to obtain a mixed solution; 6g of aluminum oxide, 1g of acrylic acid and 10ml of isopropanol were mixed and stirred, and the second precipitate, i.e., acrylic acid-coated aluminum oxide, was obtained after filtration; the initiator BPO was dissolved in ethanol to obtain an initiator solution; the second precipitate and the mixed solution were added to a three-necked flask, wherein the mass ratio of the second precipitate to the first precipitate in the mixed solution was 1:1. Then the initiator solution was added dropwise to the flask, the mass ratio of the initiator mass to the glycidyl methacrylate in the mixed solution was 0.01:1, and the reaction was carried out at 60°C for 2 hours. The solution was filtered, washed three times with methanol, and then dried in a vacuum oven at 60°C to obtain an antibacterial filler, which was recorded as aluminum oxide-AA-benzyl bromide.

[0025] Figure 1 This is the Fourier infrared spectrum of the antibacterial filler prepared in this example. In the figure, a is acrylate, b is benzyl bromide, and c is alumina-AA-benzyl bromide antibacterial filler. It can be seen that the alumina-AA-benzyl bromide antibacterial agent contains characteristic absorption peaks of acrylate and benzyl bromide.

[0026] Figure 2 This is a photograph of the alumina-AA-benzyl bromide antibacterial filler and alumina prepared in this example in a methyl methacrylate / water solution. In the figure, a is alumina and b is alumina-AA-benzyl bromide antibacterial filler. It can be seen that the alumina is precipitated in the lower layer of water, while the alumina-AA-benzyl bromide antibacterial agent filler is dissolved in the upper layer of methyl methacrylate solution, indicating that the antibacterial filler is successfully prepared.

[0027] (2) Preparation of antibacterial epoxy adhesive: 100 parts of epoxy resin E-44 and 0.5 parts of coupling agent KH-550 were mixed evenly, and then 5.5 parts of diethylenetriamine and 9 parts of triethylenetetramine were added, and finally 1 part of antibacterial filler alumina-AA-benzyl bromide was added. After the above materials were stirred evenly, the antibacterial epoxy adhesive was obtained.

[0028] Example 2 (1) Alumina-AA-benzyl bromide antibacterial filler was prepared by the same method as in Example 1.

[0029] (2) Preparation of antibacterial epoxy adhesive: 100 parts of epoxy resin E-44 and 0.5 parts of coupling agent KH-550 were mixed evenly, and then 5.5 parts of diethylenetriamine and 9 parts of triethylenetetramine were added, and finally 3 parts of antibacterial filler alumina-AA-benzyl bromide were added. After the above materials were stirred evenly, an antibacterial epoxy adhesive was obtained.

[0030] Example 3 (1) Alumina-AA-benzyl bromide antibacterial filler was prepared by the same method as in Example 1.

[0031] (2) Preparation of antibacterial epoxy adhesive: 100 parts of epoxy resin E-44 and 0.5 parts of coupling agent KH-560 were mixed evenly, and then 5.5 parts of diethylenetriamine and 9 parts of triethylenetetramine were added, and finally 5 parts of antibacterial filler alumina-AA-benzyl bromide were added. After the above materials were stirred evenly, the antibacterial epoxy adhesive was obtained.

[0032] Example 4 (1) Alumina-AA-benzyl bromide antibacterial filler was prepared by the same method as in Example 1.

[0033] (2) Preparation of antibacterial epoxy adhesive: 100 parts of epoxy resin E-44 and 0.5 parts of coupling agent KH-570 were mixed evenly, and then 5.5 parts of diethylenetriamine and 9 parts of triethylenetetramine were added, and finally 7 parts of antibacterial filler alumina-AA-benzyl bromide were added. After the above materials were stirred evenly, an antibacterial epoxy adhesive was obtained.

[0034] Example 5 (1) Alumina-AA-benzyl bromide antibacterial filler was prepared by the same method as in Example 1.

[0035] (2) Preparation of antibacterial epoxy adhesive: 100 parts of epoxy resin E-44 and 0.5 parts of coupling agent KH-580 were mixed evenly, and then 5.5 parts of diethylenetriamine and 9 parts of triethylenetetramine were added, and finally 10 parts of antibacterial filler alumina-AA-benzyl bromide were added. After the above materials were stirred evenly, the antibacterial epoxy adhesive was obtained.

[0036] Comparative Example 1 100 parts of epoxy resin E-44 and 0.5 parts of coupling agent KH-580 were mixed evenly, and then 5.5 parts of diethylenetriamine and 9 parts of triethylenetetramine were added, and the above materials were stirred evenly to obtain an epoxy adhesive.

[0037] The epoxy adhesives prepared in Examples 1-5 and Comparative Example 1 were subjected to relevant performance tests. The tensile performance test was performed according to GB / T 2567-88. After the epoxy adhesive was prepared, it was poured into a mold and cured at room temperature for 24 hours. After the curing was completed, it was tested on a universal electronic testing machine. The mechanical strength of the material when it broke was the tensile strength of the epoxy resin adhesive. The survival rate of Escherichia coli was obtained by antibacterial performance test. The test results are shown in Table 1.

[0038] Table 1

[0039] It can be seen from Table 1 that the antibacterial epoxy adhesive provided by the present invention has not only excellent antibacterial properties but also excellent tensile properties compared with the comparative example product.

[0040] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For matters that are not described in detail in some embodiments, reference may be made to the description in other embodiments.

[0041] The above-mentioned embodiments only express the implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. An antibacterial epoxy adhesive, characterized in that: The composition comprises, by weight: 100 parts of epoxy resin, 5-50 parts of curing agent, 0.1-3.0 parts of coupling agent and 1-30 parts of antibacterial filler; wherein the antibacterial filler comprises a core and an outer shell, the core is aluminum oxide, and the outer shell is formed by polymerization of benzyl bromide, acrylate, glycidyl methacrylate, triethylene glycol dimethacrylate and acrylic acid.

2. The antibacterial epoxy adhesive according to claim 1, characterized in that: The preparation method of the antibacterial filler comprises the following steps: Mixing benzyl bromide, acrylate and solvent and stirring to react to obtain a first precipitate; uniformly mixing the first precipitate with glycidyl methacrylate, triethylene glycol dimethacrylate and a solvent to obtain a mixed solution; Aluminum oxide, acrylic acid and a solvent are mixed and stirred, and solid-liquid separation is performed to obtain a second precipitate; The second precipitate, the initiator and the mixed solution are mixed and reacted, and the antibacterial filler is obtained after solid-liquid separation.

3. The antibacterial epoxy adhesive according to claim 2, characterized in that: The mass ratio of the benzyl bromide to the acrylate is 1:1 to 1:

5.

4. The antibacterial epoxy adhesive according to claim 2, characterized in that: The benzyl bromide, acrylate and solvent are mixed and stirred for reaction at a temperature of 10 to 80° C. and a reaction time of 1 to 24 h.

5. The antibacterial epoxy adhesive according to claim 2, characterized in that: The mass ratio of the first precipitate, the glycidyl methacrylate, and the triethylene glycol dimethacrylate is 1:(1-5):(1-5).

6. The antibacterial epoxy adhesive according to claim 2, characterized in that: The mass ratio of the aluminum oxide to the acrylic acid is 6:(1-20).

7. The antibacterial epoxy adhesive according to claim 2, characterized in that: The mass ratio of the second precipitate to the first precipitate in the mixed solution is 1:1 to 1:

5.

8. The antibacterial epoxy adhesive according to claim 2, characterized in that: When the second precipitate, the initiator and the mixed solution are mixed and reacted, the reaction temperature is 10-80° C. and the reaction time is 1-24 h.

9. The antibacterial epoxy adhesive according to claim 1, characterized in that: The epoxy resin is one or more of epoxy resins E-44 and E-51; the curing agent is one or more of ethylenediamine, triethylamine, diethylenetriamine, and triethylenetetramine; and the coupling agent is one or more of silane coupling agents KH-550, KH-560, KH-570, and KH-580.

10. The method for preparing the antibacterial epoxy adhesive according to any one of claims 1 to 9, characterized in that: The following steps are involved: Evenly mixing the epoxy resin and the coupling agent to obtain a first material; Evenly mixing the first material and the curing agent to obtain a second material; The second material and the antibacterial filler are mixed evenly to obtain the antibacterial epoxy adhesive.

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